KR20150035738A - Polybutadiene having epoxy groups - Google Patents

Abstract

를 포함하는, 에폭시 기를 갖는 폴리부타디엔이며,
여기서 폴리부타디엔에 존재하는 1,3-부타디엔으로부터 유래된 단량체 단위의 전체 중 A의 비율은 10 내지 60 mol 퍼센트이고, 폴리부타디엔에 존재하는 1,3-부타디엔으로부터 유래된 단량체 단위의 전체 중 B 및 C의 비율의 합은 40 내지 90 mol 퍼센트인 폴리부타디엔, 본 발명의 폴리부타디엔의 제조 방법, 및 에폭시 기를 갖는 폴리부타디엔을 포함하는 조성물에 관한 것이다.The present invention relates to the following monomeric units A, B and C:

A polybutadiene having an epoxy group,
Wherein the ratio of A to the total of monomer units derived from 1,3-butadiene present in the polybutadiene is 10 to 60 mol percent, and B and B of the entire monomer units derived from 1,3-butadiene present in the polybutadiene C is in the range of 40 to 90 mol percent, the process for producing the polybutadiene of the present invention, and the composition comprising the polybutadiene having an epoxy group.

Description

POLYBUTADIENE HAVING EPOXY GROUPS < RTI ID = 0.0 >

The present invention relates to the following 1,3-butadiene-derived monomer unit:

A polybutadiene having an epoxy group,

Here, the ratio of A to total A in the 1,3-butadiene-derived monomer units present in the polybutadiene is 10 to 60 mol%, and the ratio of B and C in the total of 1,3-butadiene-derived monomer units present in the polybutadiene The sum of the proportions is from 40 to 90 mol percent, the process for producing the polybutadiene of the present invention, and also the composition comprising the polybutadiene having an epoxy group.

Polybutadiene is a class of very industrially important organic compounds and is produced by the polymerization of 1,3-butadiene, which can be obtained in large quantities from cracking of petroleum. They are a very interesting and important starting material for chemical synthesis at both the laboratory and industrial scale.

The polymerization of 1,3-butadiene to obtain polybutadiene can be easily carried out by the method described in the prior art, including anionic polymerization. However, the butadiene produced in many applications can not be used directly, but instead they require modification first.

Such modification may be, in particular, epoxidation with a reagent such as epichlorohydrin. The epoxide group can be used in a wide variety of different reactions, especially in reaction with anhydrides or amines. Thus, the resulting polybutadiene having an epoxy group can react with a reagent such as a diamine to form a robust plastic.

Shell Oil Company, Research Disclosure, Vol. 416, 12, 1998, page 1594 describes the preparation of butadiene polymers having epoxy groups. The polydiene diol was obtained by anionic polymerization. Poor compatibility of the products and their low functionality: 1.1 and 1.6 and 2 respectively. To improve compatibility, the reaction of glycidic acid ether with EPICURE 3140 polyamide is described.

The invention in SU195104 (Lebedev Rubber Institute) involves the synthesis of anionic polybutadiene polymers which provide "living polymers" having metal atoms of group I-III, and their use as epichlorohydrin, Is described. Before the reaction with epichlorohydrin, the "living polymer" is not isolated but the butadiene oligomer is removed. The product reacts with maleic anhydride and phthalic anhydride.

However, the process described in the prior art for the production of polybutadiene with epoxy groups has the disadvantage that polybutadiene has low processability, high viscosity and a high glass transition temperature. In addition, the products in the process described in the prior art for the production of polybutadiene with epoxy groups are poorly compatible with other components of the coating composition, especially epoxy resins.

In view of this, a fundamental object of the present invention was to provide a polybutadiene having an epoxy group and a process for producing the same, having more favorable processing characteristics, particularly a minimized viscosity and / or a glass transition temperature.

Another fundamental object of the present invention was to provide a polybutadiene having an epoxy group with maximized compatibility with other components of the coating composition, especially an epoxy resin.

These and other objects are accomplished by the subject matter of the present application, and in particular by the subject matter of the appended claims, wherein the embodiments arise from the claims.

The first aspect of the fundamental problem of this object is to provide the following 1,3-butadiene-derived monomer unit:

A polybutadiene having an epoxy group,

Here, the ratio of the total A of the 1,3-butadiene-derived monomer units present in the polybutadiene is 10 to 60 mol%

The sum of the proportions of B and C in the total of the 1,3-butadiene-derived monomer units present in the polybutadiene is solved through polybutadiene of 40 to 90 mol percent.

In a first embodiment of the first aspect, the object is to provide a process for the preparation of polybutadiene having an epoxy group in which the proportion of A, B and C in the total of the 1,3-butadiene-derived monomer units present in the polybutadiene is 10% It is solved through polybutadiene.

Also in a second embodiment of the first aspect, which is an embodiment of the first embodiment, a problem is that the proportion of A in the total 1,3-butadiene-derived monomer units present in the polybutadiene is from 15 to 30 mol% Derived monomer unit in the polybutadiene is 50 to 70 mol% and the ratio of C in the total of the 1,3-butadiene-derived monomer units present in the polybutadiene is 15 ≪ / RTI > to 30 mole percent of the polybutadiene having an epoxy group.

In a third embodiment of the first aspect, which is also an embodiment of the first or second embodiment, the problem is solved by means of a polybutadiene having an epoxy group, wherein the epoxy group has the formula (I)

(I)

Wherein X represents a linear or branched alkylene group, preferably a linear alkylene group of the formula - (CH ₂ ) _x -, wherein x is 1 to 4, more preferably 1.

In a fourth embodiment of the first aspect, which is also an embodiment of the first to third embodiments, the problem is solved by polybutadiene having 1.5 to 3, preferably 1.75 to 2.5 epoxy groups.

In a second aspect, a fundamental problem of the present invention is

a) providing a polybutadiene prepared by free-radical polymerization and having a hydroxy group,

b) reacting the polybutadiene having a hydroxy group from step a) with a monoepoxy compound in the reaction mixture,

Wherein the molar ratio of the terminal hydroxy group to the monoepoxy compound is from 10: 1 to 1:10,

The temperature is 0 to 150 캜,

Wherein the reaction time is from 0.5 to 24 hours,

c) adding an alkali metal hydroxide, an alkali metal hydrogen carbonate or an alkali metal carbonate to the reaction mixture from step b)

Wherein the polybutadiene is a polybutadiene having an epoxy group,

Herein, polybutadiene having a terminal hydroxy group is represented by the following 1,3-butadiene-derived monomer unit:

Derived monomer unit in the polybutadiene is 10 to 60 mol%, and the proportion of the total of the 1,3-butadiene-derived monomer units in the polybutadiene is 10 to 60 mol%

The sum of the proportions of B and C in the entire 1,3-butadiene-derived monomer units present in the polybutadiene is 40 to 90 mol%

The ratio of A, B and C in the entire 1,3-butadiene-derived monomer units present in the polybutadiene is preferably 10% or more,

More preferably, the proportion of the total of the 1,3-butadiene-derived monomer units present in the polybutadiene is 15 to 30 mol%, and the ratio of the total of the 1,3-butadiene-derived monomer units present in the polybutadiene to the B Is 50 to 70 mol%, and the proportion of C in the total of the 1,3-butadiene-derived monomer units present in the polybutadiene is 15 to 30 mol%

Is solved through a process for producing polybutadiene having an epoxy group.

In a first embodiment of the second aspect, the problem is that the monoepoxy compound is an epihalohydrin, preferably epichlorohydrin,? -Methyl epichlorohydrin or epibromohydrin, and an alkylene oxide, preferably Is selected from the group consisting of ethylene oxide, propylene 1,2-oxide or butylene 1,2-oxide.

In a second embodiment of the second aspect, which is also an embodiment of the first embodiment, the problem is that the molar ratio of the monoepoxy compound to the terminal hydroxy group in the reaction mixture of step b) is from 0.5 to 2, preferably from 0.9 to 1.2 In method.

In a third embodiment of the second aspect, which is also an embodiment of the first or second embodiment, the object is achieved by a process for the preparation of a compound of formula (I) wherein step b) is carried out in a solvent selected from the group consisting of room temperature to liquid aliphatic, aromatic, In the presence of at least one < / RTI >

In a fourth embodiment of the second aspect, which is also an embodiment of the first to third embodiments, the object is achieved by a process for the preparation of a compound of formula I according to step b), preferably by reacting at least one metal cation selected from the group consisting of boron, aluminum, Or a semimetallic cation and at least one anion selected from the group consisting of F ^- , Cl ^- , BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- , ClO ₄ ^- , IO ₄ ^- and NO ₃ ^- In the presence of one or more metal or semi-metal salts.

In a fifth embodiment of the second aspect which is also an embodiment of the first to fourth embodiments, the object is achieved in step c) by reacting 0.7 to 1.4 mol of alkali metal hydroxide per mole of the terminal hydroxy group in step a) , An alkali metal hydrogencarbonate or an alkali metal carbonate is added.

In a sixth embodiment of the second aspect, which is also an embodiment of the first to fifth embodiments, the object is achieved by a process which further comprises distilling off the excess monoepoxy compound after step b) and before step c) Is solved.

In a seventh embodiment of the second aspect, which is one embodiment of the third to sixth embodiments, the task is to carry out step b) in the presence of a solvent, wherein the solvent is added before step c), during step c) Is removed from the reaction mixture after step c), preferably after step c).

In an eighth embodiment of the second aspect, which is one embodiment of the third to seventh embodiments, the problem is solved by a method wherein step b) is carried out in the presence of an inert gas.

In a third aspect, a fundamental problem of the present invention is to provide a polybutadiene having an epoxy group according to one embodiment of the first aspect or the first aspect or a polybutadiene prepared by a method according to one embodiment of the second aspect or the second aspect, And also a composition comprising at least one curing agent, and optionally also at least one epoxy resin.

In a fourth aspect, a fundamental problem of the present invention is a polybutadiene having a terminal epoxy group according to one embodiment of the first aspect or the first aspect or a polybutadiene prepared by a method according to one embodiment of the second aspect or the second aspect, An adhesive composition, a sealing composition and an acoustic composition for automotive applications, a casting-resin formulation for electrical insulation, a building material, or the like, which comprises a polybutadiene having an epoxy group and at least one curing agent and optionally also at least one epoxy resin, Glass-and carbon-fiber textiles, or bonding agents in sealing compositions for adhesive bonding.

In a fifth aspect, a fundamental problem of the present invention is to provide an adhesive composition, a sealing composition and an acoustic composition for automotive applications, a casting-resin formulation for electrical insulation, an impregnation or adhesive bonding of glass- and carbon- Polybutadiene having a terminal epoxy group according to one embodiment of the first aspect or the first aspect as a binder in the sealing composition for the epoxy resin, or a polybutadiene prepared by the method according to one embodiment of the second aspect or the second aspect, Group, or a composition according to the third aspect.

In a fifth aspect, a fundamental problem of the present invention is solved by a method comprising the step of curing the composition according to the third aspect.

The present invention is based on the surprising discovery that polybutadiene prepared by starting from polybutadiene obtained by free-radical polymerization and having epoxy groups has low viscosity and glass transition temperature. Although not intending to employ any particular theory, the inventors of the present invention have found that, unlike anionic polymerization of polybutadiene, free-radical polymerization produces a polybutadiene having a high content of 1,2-vinyl as a monomer unit in the polymer, Lt; RTI ID = 0.0 > mentioned < / RTI >

The present invention relates to polybutadiene prepared by the free-radical polymerization of 1,3-butadiene, which comprises in each case 1,3-butadiene-derived monomer units A, B and C present in the polybutadiene, And the polybutadiene having an epoxy group prepared therefrom, wherein the square brackets of the chemical formulas selected here for 1,3-butadiene-derived monomer units A, B and C present in the polybutadiene are as follows: And that instead the corresponding monomer units are linked by this bond to another monomer unit or another functional group, in particular a hydroxy group or an epoxy group. Where the arrays may have monomer units A, B, and C in any desired order within the polymer. A random arrangement is preferred.

In a preferred embodiment, monomer units not derived from other monomer units, especially 1,3-butadiene, may also be present with the 1,3-butadiene-derived monomer units A, B and C present in the polybutadiene. However, in the most preferred embodiment, the total of the 1,3 butadiene-derived monomer units A, B, and C present in the polybutadiene is the sum of 1,3-butadiene-derived units and monomer units incorporated into the polymer comprising other units Represents a proportion of at least 80 mole percent, preferably at least 90 mole percent, more preferably at least 95 mole percent, and most preferably at least 100 mole percent of the total.

The polybutadiene of the present invention having an epoxy group or the polybutadiene prepared by the process of the present invention and having an epoxy group is almost colorless and has a low viscosity. The viscosity is preferably determined using a rotational viscometer from Haake at 20 占 폚.

In a preferred embodiment, the polybutadiene having an epoxy group of the present invention or the polybutadiene prepared by the process of the present invention and having an epoxy group has an average functionality of 1.5 to 3, preferably 1.75 to 2.5. In a more preferred embodiment, this means that the polybutadiene molecule has an average of 1.5 to 3, preferably 1.75 to 2.5, epoxy groups irrespective of its length.

The process of the present invention requires, as step a), to provide a polybutadiene prepared by free-radical polymerization and having a hydroxy group. This type of polybutadiene having a hydroxy group can be prepared, for example, by polymerization of 1,3-butadiene in the presence of hydrogen peroxide, water and an organic solvent as described in EP12169794.0. In a preferred embodiment, the term "polybutadiene " as used herein means a product obtained by polymerization of monomer units having in each case two or more conjugated double bonds, wherein the ratio of monomer units that are 1,3-butadiene Are in an increasingly preferred order of 80, 85, 90, 95, 98, 99 or 99.9% or more.

In step b) of the process of the present invention, the polybutadiene having a hydroxy group is reacted with a monoepoxy compound in the presence of an inert gas. Particularly suitable monoepoxy compounds are those selected from the group consisting of epichlorohydrin, preferably epichlorohydrin, beta-methyl epichlorohydrin or epibromohydrin, or alternatively selected from alkylene oxides, Is selected from the group consisting of ethylene oxide, propylene 1,2-oxide and butylene-1,2-oxide. It is preferable to use epichlorohydrin in an amount of 0.5 to 2 mol per equivalent of the polybutadiene-bonded hydroxy group. It is particularly preferable to use epichlorohydrin in an amount of 0.9 to 1.2 mol per equivalent of the polybutadiene-bonded hydroxy group.

In a preferred embodiment, step b) is carried out in a solvent. In a preferred embodiment, the solvent is selected from the group consisting of room temperature to liquid aliphatic such as hexane, heptane, octane, cyclohexane, room temperature - (25 캜) - liquid aromatics such as benzene, toluene, Acetate, butyl acetate, or room-temperature-liquid ethers such as diethyl ether and diisopropyl ether, dioxane and tetrahydrofuran. The nature and amount of the solvent depends on the polybutadiene having the hydroxy group used and on the amount of the monoepoxy compound. Solvent mixtures of the mentioned solvents are possible in any desired quantitative ratio. The total proportion of polybutadiene and monoepoxy compounds having hydroxy groups in the reaction mixture may in each case be from 5 to 80 weight percent.

The reaction is carried out in the presence of an inert gas at reduced or elevated pressure. In a preferred embodiment, the expression "inert gas " as used herein means a gas or gas mixture which is totally inert. The inert gas is preferably nitrogen, a rare gas or a mixture thereof.

The duration of step b) is preferably 0.5 to 24 hours.

The temperature in step b) is from 0 to 150 캜, preferably from 0 to 70 캜.

A polybutadiene or monoepoxy compound having a hydroxy group can be used as an initial filler when starting the reaction in step b). Alternatively, it is also possible to use the two compounds together as an initial charge. The reaction mixture is then heated to the reaction temperature.

It is preferred to proceed step b) in the presence of a metal or semimetal salt as catalyst. This is preferably one or more metals of the periodic table selected from the group consisting of boron, aluminum, zinc and tin, and one or more metals of the Periodic Table selected from the group consisting of F ^- , Cl ^- , BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- ClO ₄ ^- is one or more anions from the group consisting of ^-, IO ₄ ^-, and NO _3. The amount of catalyst used is preferably from 0.001 to 0.5 mol of metal salt per equivalent of polybutadiene-bonded hydroxy groups. Reactants and catalysts are used as initial fillers and can be reacted at this time. It is preferable to use a metal salt catalyst together with a polybutadiene having a hydroxy group as an initial filler and then add a monoepoxy compound, preferably epihalohydrin.

It is preferred to remove the excess monoepoxy compound by distillation after step b), wherein it is preferred to add the solvent only after the removal of the excess monoepoxy compound.

The dehydrohalogenation in step c) is achieved by adding one or more alkali metal hydroxides as the base to the reaction mixture from step b) to form alkali metal halides. In a preferred embodiment, the amount of alkali metal hydroxide added is from 0.7 to 1.4 mol per equivalent of polybutadiene-bonded hydroxy groups. The temperature in step c) should be between 0 and 80 ° C.

The polybutadiene having an epoxy group of the present invention can be used according to the present invention in a composition comprising a polybutadiene having an epoxy group and also at least one curing agent and optionally further at least one epoxy resin.

In a preferred embodiment, the expression "epoxy resin" as used herein means a prepolymer having two or more epoxy groups per molecule. The reaction of the resin (also referred to as a curing agent) having a plurality of crosslinking agents produces a crosslinked polymer. These polymers can be thermosetting materials and can be used in fields such as civil engineering (construction), especially industrial floors, sealing systems and concrete-repair products, composites (fiber-composites), potting compositions, coating materials and adhesives. An overview of resins and hardeners, as well as their use in the civil engineering field, including their properties, is described in [H. Schuhmann, "Handbuch Betonschutz durch Beschichtungen" [Handbook of concrete protection by coatings], Expert Verlag 1992, p. 396-428. The use of resins and curing agents for the composite field is described in [P. K. Mallick, "Fiber-Reinforced Composites, Materials, Manufacturing, and Design ", CRC Press, p. 60-76. The epoxy resin used in accordance with the invention may be any of the epoxy resins that can be cured by the amine. In the epoxy resin, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, or a cyclo aliphatic type such as 3,4-epoxycyclohexyl epoxy ethane or 3,4-epoxycyclohexylmethyl 3,4 - epoxycyclohexanecarboxylate as a base. In the composition of the present invention, an epoxy resin based on bisphenol A diglycidyl ether, an epoxy resin based on bisphenol F diglycidyl ether, and a cyclo aliphatic type such as 3,4-epoxycyclohexyl epoxy ethane or Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. It is preferable to use at least one epoxy resin selected from the group consisting of bisphenol A-based epoxy resin and bisphenol F-based epoxy resin Particularly preferred. Compounds of this type are commercially available.

The curing agent used may be any of the curing agents described in the prior art for the curable composition comprising one or more epoxy compounds, especially an amine-containing curing agent having at least two or more primary and / or secondary amino groups, For example, diethylenetriamine, triethylenetetramine, methylenedianiline, bis (aminocyclohexyl) methane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, tricyclododecanediamine, (Aminomethyl) amine, 1,3- and / or 1,4-bis (aminomethyl) cyclohexane, trimethylhexamethylenediamine, polyoxyethylene Alkylene amines, polyaminoamides, and reaction products of amines with acrylonitrile and a Mannich base, and also with isophoronediamine, diethylenetriamine, trimethylhexamethylenediamine, m-phenylenebis (methylamine), 1 , 3-bis Methyl) cyclohexane, methylenebis (4-aminocyclohexane), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, N-aminoethylpiperazine, polyoxyalkyleneamine, polyaminoamide , Reaction products of amines with acrylonitrile and Mannich bases.

The compositions of the present invention may also contain polybutadiene with epoxy groups, a curing agent and optionally an epoxy resin, as well as other compounds, especially solvents such as xylene or isopropanol, preferably organic acids or tertiary amines such as salicylic acid, aminoethylpiperazine, One or more reaction promoters from the group of tris- (N, N-dimethylaminomethyl) phenols and also pigments, fillers and / or additives, preferably monofunctional, bifunctional or polyfunctional room temperature- Hexane glycidic acid ether and 1,4-butane diglycidic acid ether, neopentyl diglycidic acid ether, phenylglycidic acid ether, glycidic acid ether of bersat acid , C12-C14 glycidic acid ether, C13-C15 glycidic acid ether, p-tert-butylphenylglycidic acid ether, neopentyl glycol diglycidic acid ether, A reactive diluent selected from the group of butylene diglycidic acid ether, glycerol triglycidic acid ether, pentaerythropolyglycidic acid ether, trimethylolpropane triglycidic acid ether and cresyl glycidic acid ether, and finally a modifier such as benzyl Alcohol, coumarone resin or reactive rubber.

The present invention is further illustrated by the following drawings and non-limiting embodiments, from which further features, embodiments, aspects and advantages of the present invention may be taken.

Example:

The following polybutadiene: Polyvest EP HT and polybd R-20LM (Cray Valley) with hydroxyl groups and their properties are represented by reference products (NISSO-PB G1000 , ≪ / RTI > Nippon Soda).

Polyvest EP HT having the details listed below was synthesized according to the synthesis instructions described in patent EP12169794.0.

Two products, Poly Vest EP HT and Poly bd R-20LM, were used in the preparation of polybutadiene with epoxy groups.

Selection of polybutadiene with hydroxy group

Example 1:

116.8 g (0.1 mol OH equivalent) of PolyVest EP HT dissolved in 83.2 g of toluene was added as an initial charge with 0.19 g (0.001 mol) of SnCl2 in a sulfonation flask provided with thermometer, stirrer, reflux condenser, nitrogen blanket and dropping funnel Respectively. 10.18 g (0.11 mol) of epichlorohydrin were added to the mixture with stirring at room temperature. The reaction mixture was heated to an internal temperature of 100 < 0 > C for 5 hours. The mixture was cooled to 50 < 0 > C and then 1.6 g (0.02 mol) of 50% aqueous NaOH solution and 3.6 g (0.09 mol) of crushed NaOH were added in portions within 30 minutes. The mixture was continuously stirred at 50 < 0 > C for 1 hour. The reaction mixture was filtered. The organic phase was dried over MgSO4, filtered and isolated from the solvent under vacuum. 112 g (91.5% of theory) of almost colorless polybutadiene glycidyl ether having an equivalent weight of 1840 were isolated. The viscosity of the product determined using a rotational viscometer was 14 Pa s at 20 ° C. The determined Tg value was -78 ° C. The microstructure of the polybutadiene having the hydroxy group used remained (1,2-vinyl 22%, 1,4-cis 20%, 1,4-trans 58%).

Example 2:

58.4 g (0.1 mol OH equivalent) of polybd R-20LM dissolved in 41.6 g of toluene was mixed with 0.19 g (0.001 mol) of SnCl2 in a sulfonation flask provided with thermometer, stirrer, reflux condenser, nitrogen blanket and dropping funnel, Lt; / RTI > 10.18 g (0.11 mol) of epichlorohydrin were added to the mixture with stirring at room temperature. The reaction mixture was heated to an internal temperature of 100 < 0 > C for 5 hours. The mixture was cooled to 50 < 0 > C and then 1.6 g (0.02 mol) of 50% aqueous NaOH solution and 3.6 g (0.09 mol) of crushed NaOH were added in portions within 30 minutes. The mixture was continuously stirred at 50 < 0 > C for 1 hour. The reaction mixture was filtered. The organic phase was dried over MgSO4, filtered again and isolated from the solvent under vacuum. 56.3 g (87.9% of theory) of almost colorless polybutadiene glycidyl ether having an equivalent weight of 1010 were isolated. The viscosity of the product determined using a rotational viscometer was 4.2 Pa s at 20 ° C. The determined Tg value was -71 占 폚. The microstructure of the polybutadiene having the hydroxy group used remained (1,2-vinyl 22%, 1,4-cis 20%, 1,4-trans 58%).

Example 3

58.4 g (0.1 mol OH equivalent) of polybd R-20LM dissolved in 41.6 g of toluene was mixed with 0.19 g (0.001 mol) of SnCl2 in a sulfonation flask provided with thermometer, stirrer, reflux condenser, nitrogen blanket and dropping funnel, Lt; / RTI > 10.18 g (0.11 mol) of epichlorohydrin were added to the mixture with stirring at room temperature. The reaction mixture was heated to an internal temperature of 100 < 0 > C for 5 hours. The mixture was cooled to 50 < 0 > C and then 1.6 g (0.02 mol) of 50% aqueous NaOH solution and 3.6 g (0.09 mol) of crushed NaOH were added in portions within 30 minutes. The mixture was continuously stirred at 50 캜 for 1 hour, and 50 g of toluene was mixed. Water was removed from the reaction mixture by azeotropic distillation. The reaction mixture was filtered through MgSO4 and the solvent removed in vacuo. 58.9 g (92.0% of theory) of almost colorless polybutadiene glycidyl ether having an equivalent weight of 1005 was isolated. The viscosity of the product determined using a rotational viscometer was 4 Pa s at 20 ° C. The determined Tg value was -71 占 폚. The microstructure of the polybutadiene having the hydroxy group used remained (1,2-vinyl 22%, 1,4-cis 20%, 1,4-trans 58%).

Claims (17)

The following 1,3-butadiene-derived monomer units:

A polybutadiene having an epoxy group,
Here, the ratio of the total A of the 1,3-butadiene-derived monomer units present in the polybutadiene is 10 to 60 mol%
The sum of the proportions of B and C in the entire 1,3-butadiene-derived monomer units present in the polybutadiene is 40 to 90 mol%
Wherein the epoxy group has the formula < RTI ID = 0.0 > (I) &lt; / RTI &gt;
(I)

Wherein X represents a linear or branched alkylene group, preferably a linear alkylene group of the formula - (CH ₂ ) _x -, wherein x is 1 to 4, more preferably 1. The polybutadiene according to claim 1, wherein the proportion of A, B and C in the total of the 1,3-butadiene-derived monomer units present in the polybutadiene is 10% or more in each case independently of each other. The polybutadiene according to claim 1 or 2, wherein the proportion of the total A of the 1,3-butadiene-derived monomer units present in the polybutadiene is from 15 to 30 mol percent and the content of the 1,3-butadiene- Wherein the proportion of B in the total monomer units is 50 to 70 mol%, and the proportion of C in the total 1,3-butadiene-derived monomer units present in the polybutadiene is 15 to 30 mol%. 4. Polybutadiene according to any one of claims 1 to 3 having an average of 1.5 to 3, preferably 1.75 to 2.5 epoxy groups, regardless of length. a) providing a polybutadiene prepared by free-radical polymerization and having a hydroxy group,
b) reacting the polybutadiene having a hydroxy group from step a) with a monoepoxy compound in the reaction mixture,
Wherein the molar mass ratio of the terminal hydroxy group to the monoepoxy compound is from 10: 1 to 1:10,
The temperature is 0 to 150 캜,
Wherein the reaction time is from 0.5 to 24 hours,
c) adding an alkali metal hydroxide, an alkali metal hydrogen carbonate or an alkali metal carbonate to the reaction mixture from step b)
Wherein the polybutadiene is a polybutadiene having an epoxy group,
Wherein the terminal hydroxy group-containing polybutadiene has the following monomer units:

Derived monomer unit in the polybutadiene is 10 to 60 mol%, and the proportion of the total of the 1,3-butadiene-derived monomer units in the polybutadiene is 10 to 60 mol%
The sum of the proportions of B and C in the entire 1,3-butadiene-derived monomer units present in the polybutadiene is 40 to 90 mol%
The ratio of A, B and C in the entire 1,3-butadiene-derived monomer units present in the polybutadiene is preferably 10% or more,
More preferably, the proportion of the total of the 1,3-butadiene-derived monomer units present in the polybutadiene is 15 to 30 mol%, and the ratio of the total of the 1,3-butadiene-derived monomer units present in the polybutadiene to the B Is 50 to 70 mol%, and the proportion of C in the total of the 1,3-butadiene-derived monomer units present in the polybutadiene is 15 to 30 mol%
A process for producing polybutadiene having an epoxy group. 6. The composition of claim 5, wherein the monoepoxy compound is epihalohydrin, preferably epichlorohydrin, beta -methyl epichlorohydrin or epibromohydrin, and an alkylene oxide, preferably ethylene oxide, Propylene 1,2-oxide or butylene 1,2-oxide. The process according to claim 5 or 6, wherein the molar mass ratio of the monoepoxy compound to the terminal hydroxy group in the reaction mixture in step b) is from 0.5 to 2, preferably from 0.9 to 1.2. 8. A process according to any one of claims 5 to 7, wherein step b) is carried out in the presence of a solvent, preferably selected from the group consisting of room temperature-liquid aliphatic, aromatic, ester and ether. The method of claim 5 according to any one of claim 8, wherein the step b) the, preferably boron, aluminum, zinc and tin group at least one metal cation or metalloid cation selected from the consisting of, and F ^-, Cl ^-, In the presence of at least one metal salt or semi-metal salt comprising at least one anion selected from the group consisting of BF ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- , ClO ₄ ^- , IO ₄ ^- and NO ₃ ^- How it is. 10. The process according to any one of claims 5 to 9, wherein in step c) the alkali metal hydroxides, alkali metal hydrogencarbonates or alkali metal carbonates in an amount of 0.7 to 1.4 mol per mole of terminal hydroxyl groups in step a) How to do it. 11. The process according to any one of claims 5 to 10, further comprising distilling off the excess monoepoxy compound after step b) and before step c). Process according to any one of claims 8 to 11, wherein step b) is carried out in the presence of a solvent and the solvent is subjected to a reaction before step c), during step c) or after step c), preferably after step c) &Lt; / RTI &gt; 13. A process according to any one of claims 8 to 12, wherein step b) is carried out in the presence of an inert gas. A polybutadiene having an epoxy group according to any one of claims 1 to 4 or a polybutadiene prepared by a process according to any one of claims 5 to 13 and having an epoxy group and comprising at least one curing agent , And optionally also at least one epoxy resin. A polybutadiene having a terminal epoxy group according to any one of claims 1 to 4 or a polybutadiene prepared according to any one of claims 5 to 13 and having a terminal epoxy group, Adhesive compositions, sealing compositions and acoustical compositions for automotive applications, optionally including one or more epoxy resins, casting-resin formulations for electrical insulation, impregnation or adhesive bonding of glass- and carbon-fiber textiles for building materials &Lt; / RTI &gt; As a binder in a sealing composition for the impregnation or adhesive bonding of glass- and carbon-fiber textiles, for building materials, for casting-resin formulations for electrical insulation, for building materials, Polybutadiene having a terminal epoxy group according to any one of claims 1 to 4 or polybutadiene having a terminal epoxy group prepared by the process according to any one of claims 5 to 13 or polybutadiene having a terminal epoxy group according to claim 15 Use of the composition. 16. A method comprising curing a composition according to claim 14.